The presence of large deposits of oil shale in the Rocky Mountain region of the United States has given rise to extensive efforts to develop methods of recovering shale oil from kerogen in the oil shale deposits. It should be noted that the term "oil shale" as used in the industry is in fact a misnomer; it is neither shale nor does it contain oil. It is a sedimentary formation comprising marlstone deposit with layers containing an organic polymer called "kerogen", which upon heating decomposes to produce hydrocarbon liquid and gaseous products. It is the formation containing kerogen that is called "oil shale" herein, and the liquid hydrocarbon product is called "shale oil".
A number of methods have been proposed for processing oil shale which involve either first mining the kerogen bearing shale and processing the shale above ground, or processing the shale in situ. The latter approach is preferable from the standpoint of environmental impact since the spent shale remains in place, reducing the chance of surface contamination and the requirement for disposal of solid waste.
The recovery of liquid and gaseous products from oil shale deposits has been described in several patents, one of which is U.S. Pat. No. 3,661,423, issued May 9, 1972 to Donald E. Garrett, assigned to the assignee of this application, and incorporated in its entirety herein by this reference. This patent describes in situ recovery of liquid and gaseous hydrocarbon materials from a subterranean formation containing oil shale by mining out a portion of the subterranean formation and then fragmenting and expanding a portion of the remaining formation to form a fragmented, stationary, permeable mass of formation particles containing oil shale, referred to herein as an in situ oil shale retort. Hot retorting gases are passed through the in situ oil shale retort to convert kerogen contained in the oil shale to liquid and gaseous products.
One method of supplying hot retorting gases used for converting kerogen contained in the oil shale, as described in U.S. Pat. No. 3,661,423, includes establishment of a combustion zone in the retort and introduction of a combustion zone feed containing oxygen downwardly into the combustion zone to advance the combustion zone downwardly through the retort. The combustion zone feed can contain steam provided by a steam generator to improve efficiency of retorting. In the combustion zone oxygen in the combustion zone feed is depleted by reaction with hot carbonaceous materials to produce heat and combustion gas. By the continued introduction of the oxygen supplying combustion zone feed downwardly into the combustion zone, the combustion zone is advanced downwardly throught the retort.
The effluent gas from the combustion zone comprises combustion gas and any gaseous portion of the combustion zone feed that does not take part in the combustion process. This effluent gas passes through the retort on the advancing side of the combustion zone to heat the oil shale in a retorting zone to a temperature sufficient to produce kerogen decomposition, called retorting, in the oil shale to gaseous and liquid hydrocarbon products and a residue of solid carbonaceous material.
The liquid products and gaseous products are cooled by cooler oil shale fragments in the retort on the advancing side of the retorting zone. An off gas containing combustion gas generated in the combustion zone, product gas produced in the retorting zone, gas from carbonate decomposition, and any gaseous combustion zone feed that does not take part in the combustion process is withdrawn to the surface. Liquid hydrocarbon products, together with water produced in or added to the retort, are also withdrawn to the surface as a liquid product stream through an access tunnel, drift or shaft. The liquid hydrocarbon products are separated from the water in the liquid product stream using methods such as decanting.
Water recovered from the retorting operation can contain up to about 1% by volume of shale oil and related hydrocarbons. The presence of hydrocarbons in the water renders it useless for many applications without costly purification. Disposal of blowdown from the unit used for generation of steam for introduction to the retort as part of the oxygen supplying gaseous feed mixture can be a problem. Because the blowdown is heavily contaminated by dissolved and suspended mineral solids, it is useless for many applications without costly purification.
Methods proposed for purifying water recovered as liquid product from retorting and steam generator blowdown include use of settling basins, filters, screens, skimmers, flocculating agents, trickling filters, biofilters, osmotic filters, ion exchange resins and the like. However, all these methods require investment in capital equipment and maintenance and operating expenses. Furthermore, it is sometimes desired simply to dispose of heavily contaminated water.
Therefore, there is a need for a simple, inexpensive, economical method for removing impurities from water such as dissolved and suspended hydrocarbons contained in water from retorting oil shale and solids contained in steam generator blowdown. There is also a need for an economical method of generating steam from water containing impurities without the need for first purifying the water and without the use of additional scarce fossil fuels. In addition, there is a need for a way of disposing of contaminated water.
The present invention concerns a method having the above features for generating steam from water containing impurities, for removing impurities from water, and/or for disposing of water containing impurities. According to this method, an in situ fragmented permeable mass of particles containing treated oil shale in an in situ oil shale retort in a subterranean formation containing oil shale is provided by excavating a first portion of formation to form at least one void within the boundaries of an in situ oil shale retort site; explosively expanding a second portion of formation within the boundaries of the in situ oil shale retort site toward such a void to form a fragmented permeable mass of formation particles containing oil shale in such an in situ oil shale retort; and retorting the particles containing oil shale in the fragmented mass to produce an in situ fragmented permeable mass of particles containing treated oil shale.
Water containing hydrocarbon impurities or suspended solids impurities is introduced into such a fragmented permeable mass of particles containing treated oil shale, i.e. retorted or combusted oil shale or both, in a spent in situ oil shale retort, and water having a lower concentration of impurities can be withdrawn either as steam or as liquid water. When the fragmented permeable mass is still hot from retorting, steam is generated. When the fragmented permeable mass is cool, or has cooled in the process of steam generation, liquid water having a lower concentration of impurities than the introduced water can be withdrawn from the mass of particles, or the water can be left in the mass of particles for disposal.
This method is useful for removing hydrocarbon impurities from water such as water separated from a liquid product stream obtained by retorting oil shale. This method is also useful for removing solids from water such as blowdown obtained from a steam generator used for providing steam for retorting oil shale.
It is useful for generating steam from water containing dissolved or undissolved hydrocarbons or dissolved or undissolved mineral impurities without the need for first purifying the water, and also for disposing of such water when desired. In a preferred embodiment, steam containing hydrocarbons is generated from water containing hydrocarbon impurity by introducing such water into a hot spent retort, and the steam is introduced into an active retort as part of the combustion zone feed. The hydrocarbon content of the steam is thereby utilized as fuel in the combustion zone of the active retort.
The fragmented permeable mass of particles is contained in an in situ oil shale retort in a subterranean formation containing oil shale. Since the fragmented mass containing treated oil shale remains in place under ground, the chance of surface contamination by the impurities removed from the water is reduced.